1,4-Dioxane → HCID 54570789, compound

HRID 1369276Notes

Reaction equation

HRID 1369276 reaction equation
COC(=O)[CH2:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9](OS(C(F)(F)F)(=O)=O)=[CH:8][C:7]=1[P:20]([O:25][CH2:26][CH3:27])([O:22][CH2:23][CH3:24])=[O:21].C([Sn](CCCC)(CCCC)CCCC)=C.[Li+].[Cl-].C(C1C=C(C)C=[C:52]([C:57](C)(C)C)[C:51]=1[OH:61])(C)(C)C.[O:62]1CCOC[CH2:63]1>CCOCC.[F-].[K+].Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:63][O:62][C:51](=[O:61])[CH2:52][CH2:57][C:9]1[CH:10]=[CH:11][C:6]([CH:5]=[CH2:4])=[C:7]([P:20]([O:22][CH2:23][CH3:24])([O:25][CH2:26][CH3:27])=[O:21])[CH:8]=1

Participants

9

Reactant 5

HCID 312751,4-DioxaneHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 131723924HCID 131723924, compound

Product 1

HCID 54570789HCID 54570789, compoundYield 65%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolventHCID 522689Potassium FluorideSolvent

Conditions

Temperature
98 °C

Procedure

3-(3-(diethoxyphosphoryl-4-trifluoromethanesulfonyloxy-pheny)-propionic acid methyl ester (1 g, 223 mmol) was dissolved in dry dioxane 25 mL together with vinyl tributyltin (0.67 mL, 229 mmol), LiCl (283 mg, 6.7 mmol), Pd(PPh3)2Cl2 (47 mg, 0.067 mmol) and a crystal of 2,6-di-tert-butyl-4-methylphenol. Reaction mixture was degassed with Argon and heated to 98° C. and stirred for 2 hrs. Reaction mixture was cooled to rt and diluted with excess ether and 10 mL saturated aqueous KF solution and stirred at rt overnight. The reaction mixture was filtered through celite and separated organic layer was washed with 1 N HCl, brine, dried Na2SO4 and concentrated. Brownish oil was purified by flash column chromatography (EtOAc/hexane 90:10, Rf=0.50) to give an oil 470 mg (yield 65%).

Workup

  1. customReaction mixture
  2. customwas degassed with Argon
  3. customReaction mixture
  4. temperaturewas cooled to rt
  5. stirringstirred at rt overnight
  6. filtrationThe reaction mixture was filtered through celite
  7. customseparated organic layer
  8. washwas washed with 1 N HCl, brine, dried Na2SO4
  9. concentrationconcentrated
  10. customBrownish oil was purified by flash column chromatography (EtOAc/hexane 90:10, Rf=0.50)

Sources & evidence

ORD record
ord-3023fa1774804b1d8a211ccd86ece983
Source dataset
uspto-grants-2003_06
Patent number
US06576766B1

Reaction notes

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